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Two dimensional (2D) crystals have attracted strong interest as a new class of proton conducting materials that can block atoms, molecules and ions while allowing proton transport through the atomically thin basal planes. Although 2D materials exhibit this perfect selectivity, the reported proton conductivities have been relatively low. Here we show that vacancy-rich titania monolayers are highly permeable to protons while remaining impermeable to helium with proton conductivity exceeding 100 S cm-2 at 200 C and surpassing targets set by industry roadmaps. The fast and selective proton transport is attributed to an extremely high density of titanium-atom vacancies (one per square nm), which effectively turns titania monolayers into angstrom-scale sieves. Our findings highlight the potential of 2D oxides as membrane materials for hydrogen-based technologies.

Two-dimensional (2D) materials offer a prospect of membranes that combine negligible gas permeability with high proton conductivity and could outperform the existing proton exchange membranes used in various applications including fuel cells. Graphene oxide (GO), a well-known 2D material, facilitates rapid proton transport along its basal plane but proton conductivity across it remains unknown. It is also often presumed that individual GO monolayers contain a large density of nanoscale pinholes that lead to considerable gas leakage across the GO basal plane. Here we show that relatively large, micrometer-scale areas of monolayer GO are impermeable to gases, including helium, while exhibiting proton conductivity through the basal plane which is nearly two orders of magnitude higher than that of graphene. These findings provide insights into the key properties of GO and demonstrate that chemical functionalization of 2D crystals can be utilized to enhance their proton transparency without compromising gas impermeability.

Graphite is one of the most chemically inert materials. Its elementary constituent, monolayer graphene, is generally expected to inherit most of the parent material's properties including chemical inertness. Here we show that, unlike graphite, defect-free monolayer graphene exhibits a strong activity with respect to splitting molecular hydrogen, which is comparable to that of metallic and other known catalysts for this reaction. We attribute the unexpected catalytic activity to surface corrugations (nanoscale ripples), a conclusion supported by theory. Nanoripples are likely to play a role in other chemical reactions involving graphene and, because nanorippling is inherent to atomically thin crystals, can be important for two dimensional materials in general.

Despite being only one-atom thick, defect-free graphene is considered to be completely impermeable to all gases and liquids. This conclusion is based on theory and supported by experiments that could not detect gas permeation through micrometre-size membranes within a detection limit of 10^5 to 10^6 atoms per second. Here, using small monocrystalline containers tightly sealed with graphene, we show that defect-free graphene is impermeable with an accuracy of eight to nine orders of magnitude higher than in the previous experiments. We could discern permeation of just a few helium atoms per hour, and this detection limit is also valid for all other tested gases (neon, nitrogen, oxygen, argon, krypton and xenon), except for hydrogen. Hydrogen shows noticeable permeation, even though its molecule is larger than helium and should experience a higher energy barrier. The puzzling observation is attributed to a two-stage process that involves dissociation of molecular hydrogen at catalytically active graphene ripples, followed by adsorbed atoms flipping to the other side of the graphene sheet with a relatively low activation energy of about 1.0 electronvolt, a value close to that previously reported for proton transport. Our work provides a key reference for the impermeability of two-dimensional materials and is important from a fundamental perspective and for their potential applications.

We report physical and structural properties of single-crystal Ca2Ru1-xFexO4 (0

The orthorhombic perovskite SrIrO3 is a semimetal, an intriguing exception in iridates where the strong spin-orbit interaction coupled with electron correlations tends to impose a novel insulating state. We report results of our investigation of bulk single-crystal Sr0.94Ir0.78O2.68 or Ir-deficient, orthorhombic perovskite SrIrO3. It retains the same crystal structure as stoichiometric SrIrO3 but exhibits a sharp, simultaneous antiferromagnetic (AFM) and metal-insulator (MI) transition at 185 K. Above it, the basal-plane resistivity features an extended regime of almost linear-temperature dependence up to 800 K but the strong electronic anisotropy renders an insulating behavior in the out-of-plane resistivity. The Hall resistivity undergoes an abrupt sign change and grows below 40 K, which along with the Sommerfeld constant of 20 mJ/mole K2 suggests a multiband effect. All results including our first-principles calculations underscore a delicacy of the metallic state in SrIrO3 that is in close proximity to an AFM insulating state. The contrasting ground states in isostructural Sr0.94Ir0.78O2.68 and SrIrO3 illustrate a critical role of even slight lattice distortions in rebalancing the ground state in the iridates. Finally, the observed simultaneous AFM and MI transitions reveal a direct correlation between the magnetic transition and formation of a charge gap in the iridate, which is conspicuously absent in Sr2IrO4., Comment: 5 figures

Sr2IrO4 is a spin-orbit coupled insulator with an antiferromagnetic (AFM) transition at TN=240 K. We report results of a comprehensive study of single-crystal Sr2Ir1-xTbxO4. This study found that mere 3% (x=0.03) tetravalent Tb4+(4f7) substituting for Ir4+ (rather than Sr2+) completely suppresses the long-range collinear AFM transition but retains the insulating state, leading to a phase diagram featuring a decoupling of magnetic interactions and charge gap. The insulating state at x=0.03 is characterized by an unusually large specific heat at low temperatures and an incommensurate magnetic state having magnetic peaks at (0.95, 0, 0) and (0, 0.95, 0) in the neutron diffraction, suggesting a spiral or spin density wave order. It is apparent that Tb doping effectively changes the relative strength of the SOI and the tetragonal CEF and enhances the Hund's rule coupling that competes with the SOI, and destabilizes the AFM state. However, the disappearance of the AFM accompanies no metallic state chiefly because an energy level mismatch for the Ir and Tb sites weakens charge carrier hopping and renders a persistent insulating state. This work highlights an unconventional correlation between the AFM and insulating states in which the magnetic transition plays no critical role in the formation of the charge gap in the iridate., Comment: 8 figures

BaIrO3 is a magnetic insulator driven by the spin-orbit interaction (SOI), whereas BaRuO3 is a paramagnet and exhibits a crossover from a metallic to an insulating regime. Our investigation of structural, magnetic, transport and thermal properties reveals that substitution of Ru4+ (4d4) ions for Ir5+ (5d5) ions in BaIrO3 reduces the magnitudes of the SOI and a monoclinic structural distortion, and rebalances the competition between the SOC and the lattice degrees freedom to generate a rich phase diagram for BaIr1-xRuxO3 (0< x <1). There are two major effects of Ru additions: (1) Light Ru doping (0 < x < 0.15) prompts simultaneous, precipitous drops in both the magnetic ordering temperature TN and the electrical resistivity, which exhibits a crossover behavior from a metallic to an insulating state near TN. (2) Heavier Ru doping (0.41< x < 0.9) induces a robust metallic state with a strong spin frustration generated by competing antiferromagnetic and ferromagnetic interactions., Comment: 6 figures

Sr2IrO4 is a magnetic insulator assisted by strong spin-orbit coupling (SOC) whereas the Sr2RuO4 is a p-wave superconductor. The contrasting ground states have been shown to result from the critical role of the strong SOC in the iridate. Our investigation of structural, transport, and magnetic properties reveals that substituting 4d Ru4+ (4d4) ions for 5d Ir4+(5d5) ions in Sr2IrO4 directly adds holes to the t2g bands, reduces the SOC and thus rebalances the competing energies in single-crystal Sr2Ir1-xRuxO4. A profound effect of Ru doping driving a rich phase diagram is a structural phase transition from a distorted I41/acd to a more ideal I4/mmm tetragonal structure near x=0.50 that accompanies a phase transition from an antiferromagnetic-insulating state to a paramagnetic-metal state. We also make a comparison drawn with Rh doped Sr2IrO4, highlighting important similarities and differences., Comment: 18 pages,7 figures

We have synthesized and studied single-crystal Ba5AlIr2O11 that features dimer chains of two inequivalent octahedra occupied by tetravalent and pentavalent ions, respectively. Ba5AlIr2O11 is a Mott insulator that undergoes a subtle structural phase transition near 210 K and a magnetic transition at 4.5 K; the latter transition is surprisingly resistant to applied magnetic fields up to 12 T, but sensitive to modest applied pressure. All results indicate that the phase transition at 210 K signals an enhanced charge order that induces electrical dipoles and strong dielectric response near 210 K. It is clear that the strong covalency and spin-orbit interaction (SOI) suppress double exchange in Ir dimers and stabilize a novel magnetic state. The behavior of Ba5AlIr2O11 therefore provides unique insights into the physics of SOI along with strong covalency in competition with double exchange interactions of comparable strength., Comment: 6 figures, 20 pages. arXiv admin note: text overlap with arXiv:1505.00877

We report structural, magnetic, transport and thermal properties of single-crystal Ca2Ru1-xIrxO4 (0 < x< 0.65). Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator transition at TMI = 357 K, which is well separated from antiferromagnetic order at TN = 110 K. Substitution of 5d element, Ir, for Ru enhances spin-orbit coupling (SOC) and locking between the structural distortions and magnetic moment canting. In particular, Ir doping intensifies the distortion or rotation of Ru/IrO6 octahedra and induces weak ferromagnetic behavior along the c-axis. Moreover, the magnetic ordering temperature TN increases from 110 K at x = 0 to 215 K with enhanced magnetic anisotropy at x = 0.65. The effect of Ir doping sharply contrasts with that of 3d-element doping such as Cr, Mn and Fe, which suppresses TN and induces unusual negative volume thermal expansion. The stark difference between 3d- and 5d-element doping underlines a strong magnetoelastic coupling inherent in the Ir-rich oxides., Comment: 15 pages, 5 figures

We synthesize and study single crystals of the layered honeycomb lattice Mott insulators Na2RuO3 and Li2RuO3 with magnetic Ru4+(4d4) ions. The newly found Na2RuO3 features a nearly ideal honeycomb lattice and orders antiferromagnetically at 30 K. Single-crystals of Li2RuO3 adopt a honeycomb lattice with either C2/m or more distorted P21/m below 300 K, depending on detailed synthesis conditions. We find that Li2RuO3 in both structures hosts a well-defined magnetic state, in contrast to the singlet ground state found in polycrystalline Li2RuO3. A phase diagram generated based on our results uncovers a new, direct correlation between the magnetic ground state and basal-plane distortions in the honeycomb ruthenates., Comment: 4 figures, accepted for publication in Phys. Rev. B

We synthesize and study single crystals of a new double-perovskite Sr2YIrO6. Despite two strongly unfavorable conditions for magnetic order, namely, pentavalent Ir5+(5d4) ions which are anticipated to have Jeff=0 singlet ground states in the strong spin-orbit coupling (SOC) limit, and geometric frustration in a face centered cubic structure formed by the Ir5+ ions, we observe this iridate to undergo a novel magnetic transition at temperatures below 1.3 K. We provide compelling experimental and theoretical evidence that the origin of magnetism is in an unusual interplay between strong non-cubic crystal fields and intermediate-strength SOC. Sr2YIrO6 provides a rare example of the failed dominance of SOC in the iridates., Comment: Four Figures

We report the successful synthesis of single-crystals of the layered iridate, (Na$_{1-x}$Li$_{x}$)$_2$IrO$_3$, $0\leq x \leq 0.9$, and a thorough study of its structural, magnetic, thermal and transport properties. The new compound allows a controlled interpolation between Na$_2$IrO$_3$ and Li$_2$IrO$_3$, while maintaing the novel quantum magnetism of the honeycomb Ir$^{4+}$ planes. The measured phase diagram demonstrates a dramatic suppression of the N\'eel temperature, $T_N$, at intermediate $x$ suggesting that the magnetic order in Na$_2$IrO$_3$ and Li$_2$IrO$_3$ are distinct, and that at $x\approx 0.7$, the compound is close to a magnetically disordered phase that has been sought after in Na$_2$IrO$_3$ and Li$_2$IrO$_3$. By analyzing our magnetic data with a simple theoretical model we also show that the trigonal splitting, on the Ir$^{4+}$ ions changes sign from Na$_2$IrO$_3$ and Li$_2$IrO$_3$, and the honeycomb iridates are in the strong spin-orbit coupling regime, controlled by $\jeff=1/2$ moments., Comment: updated version with more data

Sr3Ir2O7 exhibits a novel Jeff=1/2 insulating state that features a splitting between Jeff=1/2 and 3/2 bands due to spin-orbit interaction. We report a metal-insulator transition in Sr3Ir2O7 via either dilute electron doping (La3+ for Sr2+) or application of high pressure up to 35 GPa. Our study of single-crystal Sr3Ir2O7 and (Sr1-xLax)3Ir2O7 reveals that application of high hydrostatic pressure P leads to a drastic reduction in the electrical resistivity by as much as six orders of magnitude at a critical pressure, PC = 13.2 GPa, manifesting a closing of the gap; but further increasing P up to 35 GPa produces no fully metallic state at low temperatures, possibly as a consequence of localization due to a narrow distribution of bonding angles {\theta}. In contrast, slight doping of La3+ ions for Sr2+ ions in Sr3Ir2O7 readily induces a robust metallic state in the resistivity at low temperatures; the magnetic ordering temperature is significantly suppressed but remains finite for (Sr0.95La0.05)3Ir2O7 where the metallic state occurs. The results are discussed along with comparisons drawn with Sr2IrO4, a prototype of the Jeff = 1/2 insulator., Comment: five figures